Aqueous polyamine-containing carrier systems for water-insoluble materials

ABSTRACT

The present invention is drawn to a carrier composition containing: (a) at least one polyamine compound comprising at least two amino groups; (b) at least one nonionic surfactant; (c) at least one anionic silicone; and (d) at least one water-insoluble material, and wherein the composition, when combined with an aqueous phase, forms an aqueous delivery system which is both stable, and clear to slightly hazy/limpid in appearance.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 11/154,249, filed on Jun. 16, 2005, the disclosure of which isincorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to a novel carrier system based on acombination of at least one polyamine compound having at least two aminogroups, at least one nonionic surfactant, and at least one anionicsilicone, wherein the carrier system allows water-insoluble materials tobe incorporated into aqueous solutions.

Certain water-insoluble ingredients which are oftentimes desirable forthe treatment of keratinous substrates are inherently difficult toincorporate into aqueous systems such as shampoos and conditionerswithout forming a traditional emulsion in either cream or lotion form.Moreover, many of these water-insoluble ingredients suppress latheringwhich makes the use of aqueous systems such as shampoos and body washesless desirable to consumers. Even in those aqueous systems which doemploy these types of water-insoluble ingredients, their presence isminimal due to various performance drawbacks such as poor spreadability,foaming, removal and rinsing or, in the case of styling products,difficulties in removal via shampooing.

Also, when formulating clear to slightly limpid aqueous delivery systemsfor use in treating keratinous substrates, water-insoluble compounds donot lend themselves to being used therein, due to their inability tosignificantly associate with the water present in the system.

Thus, there remains a need for an aqueous delivery system which cancarry water-insoluble materials while remaining both stable and clear,to slightly limpid, in appearance.

SUMMARY OF THE INVENTION

In order to achieve these and other advantages, the present invention isdrawn to a carrier composition containing:

(a) at least one polyamine compound having at least two amino groups;

(b) at least one nonionic surfactant;

(c) at least one anionic silicone; and

(d) at least one water-insoluble material,

wherein the composition, when combined with an aqueous phase, forms anaqueous delivery system which is both stable, and clear to slightlyhazy/limpid in appearance.

In another embodiment, the present invention is also drawn to a processfor making an aqueous delivery system which is both stable, and clear toslightly limpid in appearance, involving the steps of:

-   -   (a) providing a carrier composition containing: (i) at least one        polyamine compound, (ii) at least one nonionic surfactant        and, (iii) at least one anionic silicone;    -   (b) providing at least one water-insoluble ingredient;    -   (c) optionally, heating the composition of step (a) to form a        heated mixture;    -   (d) adding (b) to either step (a), step (c) or both step (a) and        (c);    -   (e) adding an aqueous solution to either step (c) or step (d)        form a diluted mixture; and    -   (f) cooling the diluted mixture to form the aqueous delivery        system.

Finally, in yet another embodiment, the present invention is drawn to aprocess for treating a keratinous substrate by contacting the substratewith an aqueous delivery system containing the above-disclosed carriercomposition.

DETAILED DESCRIPTION

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients and/or reaction conditionsare to be understood as being modified in all instances by the term“about”.

The term “water-insoluble” means those compounds which are eithercompletely or partially insoluble in water.

The term “carried” means that the aqueous delivery system containing thewater-insoluble ingredients is both stable and clear, to slightlylimpid, in appearance.

“Amino groups” as defined herein includes primary amino groups,secondary amino groups, and tertiary amino groups, and further includesamino groups which are terminal, pendant, and intercalated in a skeletonof the at least one polyamine compound, but does not, for example,include quaternary amino groups, amido groups, imino groups, nitrilogroups, or heteroatom analogs of any of the foregoing.

“At least one” as used herein means one or more and thus includesindividual components as well as mixtures/combinations.

“Conditioning” as used herein means imparting to at least one keratinousfiber at least one property chosen from combability, manageability,moisture-retentivity, luster, shine, and softness. The state ofconditioning is evaluated by measuring, and comparing, the ease ofcombability of the treated hair and of the untreated hair in terms ofcombing work (gm-in).

“Formed from,” as used herein, means obtained from chemical reaction of,wherein “chemical reaction,” includes spontaneous chemical reactions andinduced chemical reactions. As used herein, the phrase “formed from”, isopen ended and does not limit the components of the composition to thoselisted, e.g., as component (i) and component (ii). Furthermore, thephrase “formed from” does not limit the order of adding components tothe composition or require that the listed components (e.g., components(i) and (ii)) be added to the composition before any other components.

“Hydrocarbons,” as used herein, include alkanes, alkenes, and alkynes,wherein the alkanes comprise at least one carbon, and the alkenes andalkynes each comprise at least two carbons; further wherein thehydrocarbons may be chosen from linear hydrocarbons, branchedhydrocarbons, and cyclic hydrocarbons; further wherein the hydrocarbonsmay optionally be substituted; and further wherein the hydrocarbons mayoptionally further comprise at least one heteroatom intercalated in thehydrocarbon chain.

“Silicone compound,” as used herein, includes, for example, silica,silanes, silazanes, siloxanes, and organosiloxanes; and refers to acompound comprising at least one silicon; wherein the silicone compoundmay be chosen from linear silicone compounds, branched siliconecompounds, and cyclic silicone compounds; further wherein the siliconecompound may optionally be substituted; and further wherein the siliconecompound may optionally further comprise at least one heteroatomintercalated in the silicone chain, wherein the at least one heteroatomis different from the at least one silicon.

“Substituted,” as used herein, means comprising at least onesubstituent. Non-limiting examples of substituents include atoms, suchas oxygen atoms and nitrogen atoms, as well as functional groups, suchas hydroxyl groups, ether groups, alkoxy groups, acyloxyalkyl groups,oxyalkylene groups, polyoxyalkylene groups, carboxylic acid groups,amine groups, acylamino groups, amide groups, halogen containing groups,ester groups, thiol groups, sulphonate groups, thiosulphate groups,siloxane groups, and polysiloxane groups. The substituent(s) may befurther substituted.

“Ethylene oxide group” as defined herein refers to a group of formula—CH2CH2-O—.

“Propylene oxide group” as defined herein includes groups of formula—CH2CH2CH2-O—, groups of formula (CH3)CHCH2-O—, and groups of formula—CH2(CH3)CH—O—.

“Keratinous substrate” as defined herein may be human keratinous fiber,and may be chosen from, for example, hair, eyelashes, and eyebrows, aswell as the stratum corneum of the skin and nails.

“Polymers,” as defined herein, include homopolymers and copolymersformed from at least two different types of monomers.

Advantageously, the present invention allows water-insoluble materialsor ingredients to be carried in an aqueous solution. No alcohol isrequired to render the system stable and clear, to slightly limpid, inappearance.

The carrier composition of the invention is easy to formulate and gentleon the hair, skin, or eyelashes because the surfactants used therein aregenerally mild.

The compositions and delivery systems of the present invention readilydeliver water-insoluble ingredients to the targeted keratinoussubstrate. Accordingly, these compositions and delivery systems can beused in hair shampoos, conditioners, deep treatments, hair dyeingcompositions, including oxidative dyes and bleaches, permanent wavingcompositions, curl relaxing compositions, hair setting compositions,bath and body products, sunscreens, cosmetics, skin moisturizers, andthe like.

These systems can also be used to deliver active water-insolublepharmaceutical ingredients, particularly in topical applications. Suchsystems could further help protect against oxidation and rancidity byprotecting sensitive ingredients in pharmaceuticals or foods.

Without being bound to a particular theory, the inventors believe thatthe aqueous delivery system is in the form of a microemulsion wherebythe anionic silicone forms an ion pair or pseudo-soap with the polyaminecompound having at least two amino groups which is then coupled to theaqueous solution as a mixed micelle (or other organized structure) bythe nonionic surfactant. This structure is believed to be of sufficientstability and size to provide hydrophilic regions which carry thewater-insoluble ingredients. These microemulsions range from pourableliquids to firm ringing gels.

The at least one polyamine compound of the present invention comprisesat least two amino groups. In one embodiment, the at least one polyaminecompound of the present invention comprises at least three amino groups.In one embodiment, the at least one polyamine compound of the presentinvention comprises at least four amino groups, such as greater thanfour amino groups. In one embodiment, the at least one polyaminecompound of the present invention comprises at least five amino groups,such as greater than five amino groups. In one embodiment, the at leastone polyamine compound of the present invention comprises at least sixamino groups, such as greater than six amino groups. In one embodiment,the at least one polyamine compound of the present invention comprisesat least ten amino groups, such as greater than ten amino groups.

In one embodiment of the present invention, the at least one polyaminecompound may, for example, be chosen from aminated polysaccharidescomprising at least two amino groups, such as, for example, hydrolysatesof aminated polysaccharides comprising greater than two amino groups. Inone embodiment, the at least one polyamine compound may, for example, bechosen from polymers. Suitable polymers for use as the at least oneamine compound are polymers comprising at least two amino groups asdefined herein. Non-limiting examples of suitable polymers includehomopolymers comprising at least two amino groups, copolymers comprisingat least two amino groups, and terpolymers comprising at least two aminogroups. Thus, the at least one polyamine compound comprising at leasttwo amino groups may be chosen from, for example, polymers comprising atleast two amino groups formed from (i) at least one monomer unitcomprising at least one amino group as defined herein, and, optionally,(ii) at least one additional monomer unit different from the at leastone monomer (i); and polymers comprising at least two amino groupsformed from (i) at least one monomer comprising at least two aminogroups as defined herein, and, optionally, (ii) at least one additionalmonomer unit different from the at least one monomer (i). According tothe present invention, the at least one additional monomer differentfrom the at least one monomer (i) may or may not comprise at least oneamino group as defined herein.

In one embodiment of the present invention, the at least one polyaminecompound is chosen from polyamines. As used herein, “polyamines”comprise at least two repeating units, wherein each unit comprises atleast one amino group as defined herein. In one embodiment, polyaminesare chosen from polyethyleneimines. Polyethyleneimines suitable for usein the compositions of the present invention may optionally besubstituted. Non-limiting examples of polyethyleneimines which may beused in the composition according to the present invention are theLupasol™ products commercially available from BASF. Suitable examples ofLupasol™ polyethyleneimines include Lupasol™ PS, Lupasol PL, Lupasol™PR8515, Lupasol™ G20, Lupasol™ G35 as well as Lupasol™ SC®Polythyleneimine Reaction Products (such as Lupasol™ SC-61B®, Lupasol™SC-62J®, and Lupasol™ SC-86X®). Other non-limiting examples ofpolyethyleneimines which may be used in the composition according to thepresent invention are the Epomin™ products commercially available fromAceto. Suitable examples of Epomin™ polyethyleneimines include Epomin™SP-006, Epomin™ SP-012, Epomin™ SP-018, and Epomin™ P-1000.

Polyamines suitable for use in the present invention may also be chosenfrom polyvinylamines. Examples thereof include Lupamines® 9095, 9030,9010, 5095, 1595 from BASF.

The polyamine compounds can also be substituted. An example of such acompound is PEG-15 Cocopolyamine from Cognis.

In another embodiment, the at least one polyamine compound comprising atleast two amino groups is chosen from proteins and protein derivatives.Non-limiting examples of suitable proteins and protein derivatives foruse in the present invention include those listed at pages 1701 to 1703of the C.T.F.A. International Cosmetic Ingredient Dictionary andHandbook, 8th edition, vol. 2, (2000). In one embodiment, the at leastone polyamine compound comprising at least two amino groups is chosenfrom wheat protein, soy protein, oat protein, collagen, and keratinprotein.

In one embodiment, the at least one polyamine compound comprising atleast two amino groups is not chosen from proteins and proteinderivatives. In one embodiment, the at least one polyamine compoundcomprising at least two amino groups is not chosen from compoundscomprising lysine, compounds comprising arginine, and compoundscomprising histidine. In one embodiment, the at least one polyaminecompound comprising at least two amino groups is chosen from compoundscomprising lysine, compounds comprising arginine, compounds comprisinghistidine, and compounds comprising hydroxylysine.

In the present invention, the at least one polyamine compound ispreferably used in an amount of from greater than 0% to 30% by weight,preferably from greater than 0% to 10% by weight, and more preferablyfrom greater than 0% to 5% by weight, based on the weight of thecomposition as a whole. Preferably, the carrier composition of thepresent invention, when combined with water, forms a clear solution,though the purpose of the invention is achieved just as effectively witha slightly cloudy/limpid solution.

In general, nonionic surfactants having a Hydrophilic-Lipophilic Balance(HLB) of from 8 to 20, are contemplated for use by the presentinvention. Nonlimiting examples of nonionic surfactants useful in thecompositions of the present invention are disclosed in McCutcheon's“Detergents and Emulsifiers,” North American Edition (1986), publishedby Allured Publishing Corporation; and McCutcheon's “FunctionalMaterials,” North American Edition (1992); both of which areincorporated by reference herein in their entirety.

Examples of nonionic surfactants useful herein include, but are notlimited to, alkoxylated derivatives of the following: fatty alcohols,alkyl phenols, fatty acids, fatty acid esters and fatty acid amides,wherein the alkyl chain is in the C12-C50 range, preferably in theC16-C40 range, more preferably in the C24 to C40 range, and having fromabout 1 to about 110 alkoxy groups. The alkoxy groups are selected fromthe group consisting of C2-C6 oxides and their mixtures, with ethyleneoxide, propylene oxide, and their mixtures being the preferredalkoxides. The alkyl chain may be linear, branched, saturated, orunsaturated. Of these alkoxylated non-ionic surfactants, the alkoxylatedalcohols are preferred, and the ethoxylated alcohols and propoxylatedalcohols are more preferred. The alkoxylated alcohols may be used aloneor in mixtures thereof. The alkoxylated alcohols may also be used inmixtures with those alkoxylated materials disclosed herein-above.

Other representative examples of such ethoxylated fatty alcohols includelaureth-3 (a lauryl ethoxylate having an average degree of ethoxylationof 3), laureth-23 (a lauryl ethoxylate having an average degree ofethoxylation of 23), ceteth-10 (a cetyl alcohol ethoxylate having anaverage degree of ethoxylation of 10) steareth-10 (a stearyl alcoholethoxylate having an average degree of ethoxylation of 10), andsteareth-2 (a stearyl alcohol ethoxylate having an average degree ofethoxylation of 2), steareth-100 (a stearyl alcohol ethoxylate having anaverage degree of ethoxylation of 100), beheneth-5 (a behenyl alcoholethoxylate having an average degree of ethoxylation of 5), beheneth-10(a behenyl alcohol ethoxylate having an average degree of ethoxylationof 10), and other derivatives and mixtures of the preceding.

Also available commercially are Brij® nonionic surfactants from ICISpecialty Chemicals, Wilmington, Del. Typically, Brij® is thecondensation products of aliphatic alcohols with from about 1 to about54 moles of ethylene oxide, the alkyl chain of the alcohol beingtypically a linear chain and having from about 8 to about 22 carbonatoms, for example, Brij 72 (i.e., Steareth-2) and Brij 76 (i.e.,Steareth-10).

Also useful herein as nonionic surfactants are alkyl glycosides, whichare the condensation products of long chain alcohols, e.g. C8-30alcohols, with sugar or starch polymers. These compounds can berepresented by the formula (S)n-O—R wherein S is a sugar moiety such asglucose, fructose, mannose, galactose, and the like; n is an integer offrom about 1 to about 1000, and R is a C8-30 alkyl group. Examples oflong chain alcohols from which the alkyl group can be derived includedecyl alcohol, cetyl alcohol, stearyl alcohol, lauryl alcohol, myristylalcohol, oleyl alcohol, and the like. Preferred examples of thesesurfactants are alkyl polyglucosides wherein S is a glucose moiety, R isa C8-20 alkyl group, and n is an integer of from about 1 to about 9.Commercially available examples of these surfactants include decylpolyglucoside (available as APG® 325 CS) and lauryl polyglucoside(available as APG® 600CS and 625 CS), all the above-identifiedpolyglucosides APG® are available from Cognis, Ambler, Pa. Also usefulherein are sucrose ester surfactants such as sucrose cocoate and sucroselaurate.

Other nonionic surfactants suitable for use in the present invention areglyceryl esters and polyglyceryl esters, including but not limited to,glyceryl monoesters, preferably glyceryl monoesters of C16-C22saturated, unsaturated and branched chain fatty acids such as glyceryloleate, glyceryl monostearate, glyceryl monoisostearate, glycerylmonopalmitate, glyceryl monobehenate, and mixtures thereof, andpolyglyceryl esters of C16-C22 saturated, unsaturated and branched chainfatty acids, such as polyglyceryl-4 isostearate, polyglyceryl-3 oleate,polyglyceryl-2 sesquioleate, triglyceryl diisostearate, diglycerylmonooleate, tetraglyceryl monooleate, and mixtures thereof.

Also useful herein as nonionic surfactants are sorbitan esters.Preferable are sorbitan esters of C16-C22 saturated, unsaturated andbranched chain fatty acids. Because of the manner in which they aretypically manufactured, these sorbitan esters usually comprise mixturesof mono-, di-, tri-, etc. esters. Representative examples of suitablesorbitan esters include sorbitan monooleate (e.g., SPAN® 80), sorbitansesquioleate (e.g., Arlacel® 83 from ICI Specialty Chemicals,Wilmington, Del.), sorbitan monoisostearate (e.g., CRILL® 6 from Croda,Inc., Parsippany, N.J.), sorbitan stearates (e.g., SPAN® 60), sorbitantrioleate (e.g., SPAN® 85), sorbitan tristearate (e.g., SPAN® 65),sorbitan dipalmitates (e.g., SPAN® 40), and sorbitan isostearate.Sorbitan monoisostearate and sorbitan sesquioleate are particularlypreferred emulsifiers for use in the present invention.

Also suitable for use herein are alkoxylated derivatives of glycerylesters, sorbitan esters, and alkyl polyglycosides, wherein the alkoxygroups is selected from the group consisting of C2-C6 oxides and theirmixtures, with ethoxylated or propoxylated derivatives of thesematerials being the preferred. Nonlimiting examples of commerciallyavailable ethoxylated materials include TWEEN® (ethoxylated sorbitanmono-, di- and/or tri-esters of C12 to C18 fatty acids with an averagedegree of ethoxylation of from about 2 to about 20).

Preferred nonionic surfactants are those formed from a fatty alcohol, afatty acid, or a glyceride with a C4 to C36 carbon chain, preferably aC12 to C18 carbon chain, more preferably a C16 to C18 carbon chain,derivatized to yield an HLB of at least 8. HLB is understood to mean thebalance between the size and strength of the hydrophilic group and thesize and strength of the lipophilic group of the surfactant. Suchderivatives can be polymers such as ethoxylates, propoxylates,polyglucosides, polyglycerins, polylactates, polyglycolates,polysorbates, and others that would be apparent to one of ordinary skillin the art. Such derivatives may also be mixed polymers of the above,such as ethoxylate/propoxylate species, where the total HLB ispreferably greater than or equal to 8. Preferably the nonionicsurfactants contain ethoxylate in a molar content of from 10-25, morepreferably from 10-20 moles.

The nonionic surfactant will typically be present in the composition inan amount of from greater than 0% to 70% by weight, preferably fromgreater than 0% to 40% by weight, and more preferably from greater than0% to 20% by weight, based on the weight of the composition as a whole.

In general, non-limiting examples of anionic silicones which may be usedin the present invention include silicone carboxylates, siliconephosphates, silicone sulfates, silicone sulfosuccinates, and siliconesulfonates.

Suitable silicone carboxylates may be chosen from water soluble siliconecompounds comprising at least one carboxylic acid group, oil solublesilicone compounds comprising at least one carboxylic acid group,water-dispersible silicone compounds comprising at least one carboxylicacid group, and silicone compounds comprising at least one carboxylicacid group which are soluble in organic solvents. In one embodiment, theat least one silicone compound comprising at least one carboxylic acidgroup further comprises at least one alkoxylated chain, wherein the atleast one alkoxy group may be chosen from terminal alkoxy groups,pendant alkoxy groups, and alkoxy groups which are intercalated in theskeleton of the at least one silicone compound. Non-limiting examples ofat least one alkoxy group include ethylene oxide groups and propyleneoxide groups.

The at least one carboxylic acid group may be chosen from terminalcarboxylic acid groups and pendant carboxylic acid groups. Further, theat least one carboxylic acid may be chosen from carboxylic acid groupsin free acid form, i.e., —COOH, and carboxylic acid groups in salt form,i.e., —COOM, wherein M may be chosen from inorganic cations, such as,for example, potassium cations and sodium cations, and organic cations.

In one embodiment, the at least one silicone compound comprising atleast one carboxylic acid group is chosen from silicone compounds offormula (I) and salts thereof:

wherein: a is an integer ranging from 1 to 100; b is an integer rangingfrom 0 to 500; R, which may be identical or different, are each chosenfrom optionally substituted hydrocarbon groups comprising from 1 to 9carbon atoms, optionally substituted phenyl groups, and groups offormula (II):

wherein: c, d, and e, which may be identical or different, are eachintegers ranging from 0 to 20; EO is an ethylene oxide group; PO is apropylene oxide group; and R″ is chosen from optionally substituteddivalent hydrocarbons, such as alkylene groups and alkenylene groupscomprising from 2 to 22 carbon atoms, and optionally substituteddivalent aromatic groups, such as groups of formula (III):

and groups of formula (IV):

with the proviso that at least one of the R groups is chosen from groupsof formula (II) and with the further proviso that when only one of the Rgroups is chosen from groups of formula (II), the other R groups are notall methyl groups.

Non-limiting examples of the at least one silicone compound includethose commercially available from Noveon under the name Ultrasil® CA-1Silicone and Ultrasil® CA-2 Silicone, both of which correspond toformula (V) below. This silicone carboxylate is sold in the free acidform as an emulsifier and dispersing aid for complexing fatty cationicamines and quaternary amines. Thus, in one embodiment, the at least onesilicone compound is chosen from silicone compounds of formula (V) andsalts thereof:

wherein: a is an integer ranging from 1 to 100; b is an integer rangingfrom 0 to 500; AO is chosen from groups of formula (VI):-(EO)_(c)—(PO)_(d)-(EO)_(e)—  (VI)wherein: c, d, and e, which may be identical or different, are eachintegers ranging from 0 to 20; EO is an ethylene oxide group; and PO isa propylene oxide group; x is an integer ranging from 0 to 60; R″ ischosen from optionally substituted divalent hydrocarbons, such asalkylene groups and alkenylene groups comprising from 2 to 22 carbonatoms, and optionally substituted divalent aromatic groups, such asgroups of formula (III):

and groups of formula (IV):

Non-limiting examples of the at least one silicone compound includethose described in U.S. Pat. Nos. 5,248,783 and 5,739,371, thedisclosures of which are incorporated herein by reference, and which aresilicone compounds of formula (I).

Suitable silicone phosphates may be chosen from water-soluble siliconecompounds comprising at least one phosphate group, oil soluble siliconecompounds comprising at least one phosphate group, water-dispersiblesilicone compounds comprising at least one phosphate group, and siliconecompounds comprising at least one phosphate group which are soluble inorganic solvents.

In one embodiment, the at least one silicone compound comprising atleast one phosphate group further comprises at least one alkoxylatedchain, wherein the at least one alkoxy group may be chosen from terminalalkoxy groups, pendant alkoxy groups, and alkoxy groups which areintercalated in the skeleton of the at least one silicone compound.Non-limiting examples of at least one alkoxy group include ethyleneoxide groups (“EO”=—CH2-CH2-O—) and propylene oxide groups (“PO”═C3H6O).

The at least one phosphate group may be chosen from terminal phosphategroups and pendant phosphate groups. Further, the at least one phosphategroup may be chosen from groups of formula —O—P(O)(OH)2, groups offormula —O—P(O)(OH)(OR), and groups of formula —O—P(O)(OR)2, wherein Rmay be chosen from H, inorganic cations, and organic cations.Non-limiting examples of inorganic cations include alkali metals, suchas, for example, potassium lithium, and sodium. A non-limiting exampleof organic cations is at least one additional silicone compound whichmay be identical to or different from the at least one silicone compoundbonded to the other oxygen of the phosphate group.

In one embodiment, the at least one silicone compound comprising atleast one phosphate group is chosen from silicone compounds of formula(I):

wherein R¹, which may be identical or different, are each chosen from H,organic cations, inorganic cations, optionally substituted hydrocarbons(such as alkyl groups and alkenyl groups comprising from 1 to 22 carbonatoms), optionally substituted aromatic groups; groups of formula (II)and salts thereof:CH₃(CH₂)_(x)—O-(EO)_(c)—(PO)_(d)-(EO)_(e)—CH₂CH₂—  (II)wherein: c, and d, which may be identical or different, are eachintegers ranging from 0 to 20; e is an integer ranging from 0 to 19; andx is an integer ranging from 0 to 21; groups of formula (III) and saltsthereof:HO-(EO)_(c)—(PO)_(d)-(EO)_(e)—(CH₂)_(x)—  (III)wherein: c, d, and e, which may be identical or different, are eachintegers ranging from 0 to 20; and x is an integer ranging from 0 to 21;and groups of formula (IV) and salts thereof:

wherein: a is an integer ranging from 0 to 200; b is an integer rangingfrom 0 to 200; R′, which may be identical or different, are each chosenfrom optionally substituted hydrocarbons, such as alkyl groups andalkenyl groups comprising from 1 to 22 carbon atoms, optionallysubstituted aromatic groups, groups of formula (III) as defined aboveand salts thereof; and R, which may be identical or different, are eachchosen from optionally substituted hydrocarbons, such as alkyl groupsand alkenyl groups comprising from 1 to 22 carbon atoms, optionallysubstituted aromatic groups, optionally substituted divalenthydrocarbons, such as alkylene groups and alkenylene groups comprisingfrom 1 to 22 carbon atoms, optionally substituted divalent aromaticgroups, groups of formula (III) as defined above and salts thereof, andgroups of formula (V):-(EO)_(c)—(PO)_(d)-(EO)_(e)—(CH₂)₃—  (V)wherein:

-   the (CH₂)₃ end is bonded to the silicon of the compound of    formula (IV) and the (EO) or (PO) end, if present, is bonded to the    oxygen of the compound of formula (I); c, d, and e, which may be    identical or different, are each integers ranging from 0 to 20; EO    is an ethylene oxide group; and PO is a propylene oxide group; and    with the proviso that at least one R is chosen from groups of    formula (V) and salts thereof; and with the further proviso that at    least one R¹ is chosen from groups of formula (IV) and salts thereof    and at least one other R¹ is chosen from H, organic cations, and    inorganic cations.

Non-limiting examples of the inorganic cations include alkali metals,such as potassium, lithium, and sodium. Non-limiting examples of the atleast one silicone compound include those commercially available fromPhoenix Chemical, Inc. of New Jersey under the name of Pecosil®, such asPecosil® PS-100, Pecosil® PS-112, Pecosil® PS-150, Pecosil® PS-200,Pecosil® WDS-100, Pecosil® WDS-200, Pecosil® PS-100 B, and Pecosil®PS-100 K and those commercially available from Siltech under the nameSilphos A-100 and Silphos A-150. Other non-limiting examples of the atleast one silicone compound include those described in U.S. Pat. Nos.5,070,171, 5,093,452, and 5,149,765 the disclosures of which areincorporated herein by reference.

Suitable silicone sulfates for use in the present invention includethose represented by formula VI:

wherein R¹¹ is selected from lower alkyl having one to eight carbonatoms or phenyl, R¹² is —(CH₂)₃—O-(EO)_(x)—(PO)_(y)-(EO)_(z)—SO₃ ³¹-M⁺wherein M is a cation and is selected from Na, K, Li, or NH₄; x, y and zare integers independently ranging from 0 to 100; R¹³ is—(CH₂)₃—O-(EO)_(x)—(PO)_(y)-(EO)_(z)—H; R¹⁴ is methyl or hydroxyl; a¹and c¹ are independently integers ranging from 0 to 50; b¹ is an integerranging from 1 to 50. An example thereof is Ultrasil SA-1 siliconecommercially available from Noveon.

Suitable silicone sulfosuccinates which may be employed include, but arenot limited to, those corresponding to formula VII:

wherein R represents a divalent radical selected from

wherein a′ and b′ range from 0 to 30; x and y are such that themolecular weight ranges from 700 to 1600, and M is an alkali metal suchas sodium or potassium, or an ammonium group.

A particularly preferred anionic silicone is Dimethicone PEG-8phosphate, commercially available from Noveon under the tradenameUltrasil PE-100.

The anionic silicone is present in the composition in an amount rangingfrom greater than 0 to 50% by weight, preferably from greater than 0 to30% by weight, and more preferably from greater than 0 to 15% by weight,based on the weight of the composition as a whole.

It has surprisingly been found that the carrier composition of thepresent invention facilitates the formulation of an aqueous deliverysystem capable of carrying up to 50% by weight, preferably up to 30% byweight, more preferably up to 20% by weight, and most preferably up to10% by weight, all weights being based on the weight of the composition,of water-insoluble ingredients. The resultant aqueous delivery system isboth stable, and clear to slightly hazy/limpid in appearance.

Thus, in another aspect, the present invention relates to an aqueousdelivery system comprising the carrier composition, at least onewater-insoluble ingredient and an aqueous phase. The carrier compositionis present in an amount sufficient to allow the at least onewater-insoluble material to be incorporated into the aqueous system. Theamount sufficient for incorporation may vary depending on the type ofcomposition; for example, shampoo and mascara formulations require alower concentration of the carrier composition than do conditioner, deeptreatment, bleach, permanent wave, dye, and relaxant compositions.

Water-insoluble materials or ingredients include, but are not limitedto, the following:

(1) Lipophilic “ingredients” or “materials” such as silicones,oil-soluble vitamins such as Vitamin E and Vitamin A, sunscreens,ceramides and natural oils: The lipophilic ingredients may be in theform of sunscreens, bacteriostats, moisturizers, colors, topicalpharmaceuticals and the like. Preferred lipophilic ingredients include:Vitamin E, Vitamin E Acetate, Vitamin A Palmitate, olive oil, mineraloil, 2-oleamido-1,3-octadecanediol, octylmethoxy cinnamate, octylsalicylate, and silicones such as dimethicone, cyclomethicone, phenyltrimethicone, dimethiconol, dimethicone copolyol, aminosilicone andlaurylmethicone copolyol. The lipophilic ingredients will, for example,moisturize or condition the skin, hair, and/or eyelashes and leavebehind no oily feel.

(2) Water-insoluble polymers, resins, and latexes, wherein the polymersand resins include but are not limited to those containing carboxylmoieties, such as acrylates and other carboxy polymers.

Preferred water-insoluble ingredients for use in the present inventioninclude silicones ranging from low molecular weight fluids to highmolecular weight gums; hydrocarbons such as mineral oil, petrolatum,paraffins, iso-paraffins, aromatic hydrocarbons, and the like; plantoils such as olive, avocado, coconut, and the like; fatty acids; fattyesters; fatty alcohols; and fatty waxes.

The aqueous phase of the inventive delivery system can containadditional ingredients such as anionic surfactants, organic salts,inorganic salts, proteins, hair dyes, water-soluble polymers, quaternaryammonium compounds, complex and simple carbohydrates, amino acids,preservatives and fragrances.

Another embodiment of the present invention is drawn to a process formaking an aqueous delivery system. This process involves: (a) providinga carrier composition containing at least one polyamine compound, atleast one nonionic surfactant, and at least one anionic silicone; (b)providing at least one water-insoluble ingredient; (c) optionally,heating the carrier composition to form a heated composition; (d) addingthe water-insoluble ingredient to either the carrier composition, theheated composition or both; (e) providing an aqueous solution; (f)adding the aqueous solution to the heated mixture to form a dilutedmixture and (g) cooling the diluted mixture to form the desired aqueousdelivery system. Preferably the aqueous delivery system obtained cancarry a high load (i.e., 50% is considered a high load) of thewater-insoluble ingredient.

In another embodiment, the present invention is drawn to a process fortreating keratinous substances such as, but not limited to, hair, skin,or eyelashes by contacting the keratinous substance with theabove-disclosed aqueous delivery system. The term treating in thecontext of this invention includes, but is not limited to, shampooing,conditioning, dyeing, bleaching, permanent waving, relaxing, setting,moisturizing, and making-up, for example, applying mascara orfoundation.

As mentioned previously, the carrier composition and aqueous deliverysystem of the present invention can be used as an ingredient itself in,for example, shampoos, conditioners (rinse-off and leave-in), deeptreatments for hair, body washes, bath gels, hair dyeing compositions,permanent wave formulations, relaxers, make-up preparations,particularly mascara and foundation, and skin creams or lotions.

The aqueous delivery systems of the invention can be further associated,in the hair products described above, with proteins including hydrolyzedsoy protein, lauryldimonium hydrolyzed soy protein (cationic Soyaprotein) and wheat amino acids. The proteins could also include corn,wheat, milk, or silk proteins, collagens, keratins, or others.Furthermore, taurine and arginine hydrochloride may be associatedtherein to maximize protein binding to the keratinous substrate.Cationic proteins or proteins in general may be stabilizers for theaqueous delivery system and enhance its delivery by changing the chargeof the aqueous delivery system. The skin and the hair attract cationicingredients, and proteins are generally substantive to these tissues.

Other ingredients in the aqueous delivery system may include cationicpolymers, such as polyquaternium 4, polyquaternium 6, polyquaternium 7,polyquaternium 10, polyquaternium 11, polyquaternium 16, polyquaternium22, and polyquaternium 32, cationic conditioners, such as quaternium 27,behenamidopropyl PG-dimonium chloride, hydroxyethyl tallowdimoniumchloride, hexadimethrine chloride, stearalkonium chloride, andcetrimonium chloride, isoparaffins, sodium chloride, propylene glycol,preservatives such as phenoxyethanol, methylparaben, ethylparaben, andpropylparaben, pH adjusters such as phosphoric acid, humectants such astrehalose, and emollients such as octyldodecanol. Many other examples ofmaterials from the classes listed above would be readily known to one ofordinary skill in the art.

Further, shampoos, conditioners, and deep treatments within the scope ofthe present invention may be used on hair which has been treated, e.g.,with color (dye or bleach) or chemicals (permanent wave orstraightening), or which is dry or fine and show significantsubstantivity for the hair.

The invention will be further clarified by the following examples, whichare intended to be illustrative of the invention, but not limitingthereof.

EXAMPLES

General procedure: The general procedure for formulating the carriersystem is as follows: Add Lupasol G-35 (INCI: PEI) and Ultrasil PE-100(silicone phosphate) into a beaker and begin mixing at moderate speed.Next, add the active ingredient. Mix well. Then add Laureth-4. Mix well.Lastly, add deionized water. Mix until formula becomes clear. Note: Thismay require mixing for over 4 hours.

1. The Carrier System

Following the general procedure, a series of solutions were made asdepicted in Table 1. The results show that a complete carrier system isneeded to form a clear, stable solution that contains a water insolublesilicone.

TABLE 1 Experiments showing a clear, stable carrier system Combinationsof ingredients Appearance Water 40 g + Lupasol G-3510 g + DC 200(300,000 cst) Hazy 10 g Water 40 g + Laureth-4 10 g + DC 200 (300,000cst) 10 g Hazy Water 40 g + Silicone Phosphate 30 g + DC 200 Hazy(300,000 cst) 10 g Water 40 g + Lupasol G-35 10 g + Laureth-4 Hazy 10g + DC 200 (300,000 cst) 10 g Water 40 g + Lupasol G-35 10 g + SiliconePhosphate Hazy 30 g + DC 200 (300,000 cst) 10 g Water 40 g + Laureth-410 g + Silicone Phosphate Hazy 30 g + DC 200 (300,000 cst) 10 g Water 40g + Lupasol G-35 10 g + Laureth-4 10 g + Clear Silicone Phosphate 30 g +DC 200 (300,000 cst) 10 g2. Carrier System with Different Silicones

The carrier system is able to carry different types of silicones, suchas DC 200 (INCI: dimethicone) and DC 556 (INCI: phenyltrimethicone).When formulated using the general procedure as described above, clear,stable systems are obtained, as shown in table 2.

TABLE 2 Carrier system with different types of silicones D.I. Water 40%40% 40% 40% Lupasol G-35 10% 10% 10% 10% Laureth-4 10% 10% 10% 10%Silicone 30% 30% 30% 30% Phosphate Silicones 10% 10% (DC 200 10% (DC 20010% (DC 200 (60,000 cst)) (300,000 cst)) (DC 556) (1000 cst))3. Carrier System with Tea Tree Oil

The carrier system is able to carry different types of oils, such as teatree oil. When formulated using the general procedure as describedabove, clear, stable systems are obtained, as shown in table 3.

TABLE 3 Carrier system with Tea tree oil D.I. Water 40% Lupasol G-35 10%Laureth-4 10% Silicone Phosphate 30% Tea Tree oil 10%4. Carrier System with Esters/Waxes/Hydrocarbons

The carrier system is able to carry different types of hydrocarbons,such as C11-13 Isoparaffin. When formulated using the general procedureas described above, clear, stable systems are obtained, as shown intable 4.

TABLE 4 Carrier system with C11-13 Isoparaffin D.I. Water 40% LupasolG-35 10% Laureth-4 10% Silicone Phosphate 30% C11-13 Isoparaffin 10%5. Carrier System with Other Polyamines

Carrier system is also clear and stable when Lupasol G-35 is replacedwith another polyamine, such as Lupamin 9095, Lupasol PR 8515, LupasolP, and Lupasol SK. See table 5.

TABLE 5 Carrier system with different polyamines A B C D D.I. Water 40%40% 40% 40% Polyamines 10% 10% 10% 10% (Lupamin 9095) (Lupasol (Lupasol(Lupasol SK) PR 8515) P) Laureth-4 10% 10% 10% 10% Silicone 30% 30% 30%30% Phosphate C11-13 10% 10% 10% 10% IsoparaffinFurthermore, the above formula B is dilutable in water.6. Conditioning Effects of the Carrier System

The conditioning effect of the carrier system, as a carrier ofDimethicone, was assessed by the wet combability method using theInstron 4444 Tensile Tester. Evaluation was carried out on virgin hair,cleansed with 15% SLES, and treated a single time with the carrierformulation. Specifically, swatches were treated once with 2 g product,which remained on the hair for 1 minute. Swatches were then shampooedwith 2.5 g of 15% SLES for 15 seconds and rinsed for 10 seconds. Thetotal combing energy required to comb the hair was measured aftercleansing with SLES (W_(i)), as well as after treatment and one shampoo(W_(f)). The percent change in combing energy was calculated using thefollowing formula:% Δ Combing Energy=(W _(f) −W _(i))/(W _(i))×100%where W_(i)=combing energy required prior to treatment and W_(f)=combingenergy required after treatment and one shampoo.

Treatments, which improve wet combability, will result in negativepercent change values.

A clear, stable carrier solution composed of the following formula wasused to treat the hair:

Classification Trade Name % wt/wt Water Water 40 Silicone PhosphateUltrasil PE-100 30 Nonionic Surfactant Brij 30 10 PEI Lupasol G 35 10Dimethicone Dow Corning 200 Fluid (60,000 cst) 10

Following treatment with the carrier formulation and a single shampoo,the percent change in combing energy was −34.19%, indicating that thetreated hair is significantly more conditioned. Thus, treatment with thecarrier system made the hair more manageable and easier to comb by34.19%.

It will be apparent to those skilled in the art that variousmodifications and variations can be made in the delivery system,composition and methods of the invention without departing from thespirit or scope of the invention. Thus, it is intended that the presentinvention cover the modifications and variations of this inventionprovided that they come within the scope of the appended claims andtheir equivalents.

What is claimed is:
 1. A composition comprising: (a) at least onepolyamine compound comprising at least two amino groups; (b) at leastone nonionic surfactant; (c) at least one anionic silicone; (d) at leastone water-insoluble material which is present in an amount of about 4%by weight, or more, based on the weight of the composition; and (e)water.
 2. The composition of claim 1, wherein (a) is polyethyleneimine.3. The composition of claim 1, wherein (a) is polyvinylamine.
 4. Thecomposition of claim 1, wherein (a) is PEG-15 cocopolyamine.
 5. Thecomposition of claim 1, wherein (a) is present in an amount of fromgreater than 0 to about 30% by weight, based on the weight of thecomposition.
 6. The composition of claim 1, wherein (a) is present in anamount of from greater than 0 to about 5% by weight, based on the weightof the composition.
 7. The composition of claim 1, wherein (b) has anHLB of about 8 or greater.
 8. The composition of claim 1, wherein (b) ispresent in an amount of from greater than 0 to about 70% by weight,based on the weight of the composition.
 9. The composition of claim 1,wherein (b) is present in an amount of from greater than 0 to about 20%by weight, based on the weight of the composition.
 10. The compositionof claim 1, wherein (c) is a silicone phosphate.
 11. The composition ofclaim 1, wherein (c) is a silicone carboxylate.
 12. The composition ofclaim 1, wherein (c) is a silicone sulfate.
 13. The composition of claim1, wherein (c) is present in an amount of from greater than 0 to about50% by weight, based on the weight of the composition.
 14. Thecomposition of claim 1, wherein (c) is present in an amount of fromgreater than 0 to about 15% by weight, based on the weight of thecomposition.
 15. The composition of claim 1, wherein the water-insolublematerial is selected from the group consisting of silicones,hydrocarbons, plant oils, fatty acids, fatty esters, fatty alcohols,fatty waxes, and mixtures thereof.
 16. The composition of claim 1,wherein the water-insoluble material is a silicone.
 17. The compositionof claim 1, wherein the water-insoluble material is selected from thegroup consisting of dimethicone, cyclomethicone, phenyl trimethicone,dimethiconol, dimethicone copolyol, aminosilicone, laurylmethiconecopolyol, capric/caprylic triglyceride, avocado oil, olive oil,macadamia nut oil, jojoba oil, apricot kernel oil, rice bran oil, teatree oil, mineral oil, and mixtures thereof.
 18. The composition ofclaim 1, wherein the water is present in an amount of about 40% byweight, based on the weight of the composition.
 19. The composition ofclaim 1, further comprising at least one ingredient selected from thegroup consisting of anionic surfactants, organic salts, inorganic salts,proteins, hair dyes, water-soluble polymers, quaternary ammoniumcompounds, complex and simple carbohydrates, amino acids, preservativesand fragrances.
 20. The composition of claim 1, further comprising ananionic surfactant, and the composition is in the form of a shampoo. 21.The composition of claim 1, further comprising a hair dye, and thecomposition is in the form of a hair dye.
 22. The composition of claim1, which is in the form of a shampoo, a leave-in conditioner, arinse-off conditioner, a combination shampoo-conditioner, deep treatmentfor hair, body wash, bath gel, hair dyeing composition, permanent waveformulation, relaxer, make-up preparation, skin cream or skin lotion.23. The composition of claim 1, wherein the composition is a mascara ora foundation.
 24. A process for making an aqueous delivery system whichis both stable, and clear to slightly limpid in appearance, involvingthe steps of: (a) providing a carrier composition containing: (i) atleast one polyamine compound comprising at least two amino groups, (ii)at least one nonionic surfactant and, (iii) at least one anionicsilicone; (b) providing at least one water-insoluble ingredient; (c)optionally, heating the composition of step (a) to form a heatedmixture; (d) adding (b) to either step (a), step (c) or both step (a)and (c); (e) adding an aqueous solution to either (c) or (d) to form adiluted mixture; and (f) cooling the diluted mixture to form the aqueousdelivery system; wherein (b) is present in an amount of about 4% byweight, or more, based on the weight of the aqueous delivery system. 25.A process for treating a keratinous substrate comprising contacting thekeratinous substrate with a composition containing: (a) at least onepolyamine compound comprising at least two amino groups; (b) at leastone nonionic surfactant; (c) at least one anionic silicone; and (d) atleast one water-insoluble material which is present in an amount ofabout 4% by weight, or more, based on the weight of the composition. 26.The process of claim 25, wherein the keratinous substrate is hair. 27.The process of claim 25, wherein the keratinous substrate is skin. 28.The process of claim 25, wherein the keratinous substrate is an eyelash.